CN113278795B - Wet smelting method for high nickel matte - Google Patents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/045—Leaching using electrochemical processes
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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Abstract
The invention provides a hydrometallurgical method for high nickel matte. The smelting method comprises the following steps of S1, electrolyzing an anode containing high nickel matte to obtain a nickel-rich solution and a residual anode; and S2, carrying out oxygen pressure leaching on the anode scrap to obtain nickel-containing leachate and leaching residues. By the smelting method, firstly, the anode comprising the high nickel matte is electrolyzed, so that most of nickel in the high nickel matte enters into the electrolyte. And then, carrying out oxygen pressure leaching on the anode scrap to further enable the nickel in the anode scrap to enter the liquid, and further increasing the nickel content separated from the raw material. In the oxygen pressure leaching process, impurity ions with higher reduction potential in the leaching solution are subjected to reduction displacement with nickel by using the reduction potential difference between elements, so that the impurity ions are remained in the leaching slag as sulfides, and the nickel, the sulfur and the impurity ions are effectively separated.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a hydrometallurgical method for high nickel matte.
Background
The high nickel matte is a sulfide eutectic of metals such as nickel, copper, cobalt, iron and the like which are primarily smelted from nickel concentrate by an electric converter. The nickel-iron-nickel ore smelting process is a lump containing 50-75% of nickel, 1-15% of copper, 0.1-1.5% of cobalt, 1-5% of iron and 20-25% of sulfur, can be used for producing electrolytic nickel by an electrolytic method and producing nickel sulfate by high-pressure leaching, and because the process of converting nickel iron into nickel matte is successful recently, the nickel matte becomes an important smelting intermediate product of laterite-nickel ore and nickel sulfide ore, and is paid much attention to the field of nickel processing.
The production process of high nickel matte at home and abroad is summarized as follows: a. direct electrolysis of a high nickel matte anode, b, a high nickel matte chlorination refining process, c, a nickel concentrate reduction roasting electrolysis process, d, a high nickel matte normal pressure leaching process, e, a high nickel matte high pressure leaching process, and f, a high nickel matte oxidation roasting acid leaching process. The process related to electrolysis is basically that cathode nickel is produced by direct electrodeposition, the anode plate remained by electrolysis needs to be continuously treated by a proper matching process, and the impurity removal and purification process is relatively complex; the electrolysis process is incomplete and the leaching rate of atmospheric or pressure leaching alone is not high enough. Several methods are generally combined together to achieve better leaching effect, such as one-stage atmospheric pressure leaching and electric potential matching and two-stage pressure leaching for treating nickel matte; or the high nickel matte is treated by utilizing the technology of combining electrolysis with the first-stage normal-pressure acid leaching and the second-stage chlorine leaching, but the processes are too many and are inconvenient to operate and the cost is reduced.
Disclosure of Invention
The invention mainly aims to provide a high nickel matte hydrometallurgy method, which aims to solve the problems of complex process and high cost of electrolytic dissolution of a high nickel matte anode plate in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a high nickel matte hydrometallurgical method, which includes: step S1, electrolyzing the anode containing high nickel matte to obtain a nickel-rich solution and a residual anode; and S2, carrying out oxygen pressure leaching on the anode scrap to obtain nickel-containing leachate and leaching residues.
Further, the step S1 includes: making an electrolysis system comprising a cathode, an electrolyte and an anode produce an electrolytic reaction to obtain a nickel-rich solution and a residual anode, wherein H in the electrolyte + The concentration is 1 to 2mol/L, the volume concentration of hydrogen peroxide is 1 to 10 percent, the concentration of copper ions is 5 to 15g/L, the concentration of manganese ions is 5 to 15g/L, preferably, the electrolyte also contains sodium chloride, the concentration of the sodium chloride is 50 to 120g/L, and preferably, H in the electrolyte + Provided by sulfuric acid; preferably, the anode and the cathode each have a plurality of them, and the center distance of the same poles of each of the anode and the cathode is 10 to 30cm, and the current density of the anode is 200 to 350A/m 2 The electrolysis voltage is 2.8-4.0V, the electrolysis reaction is preferably carried out in oxygen-containing gas, the oxygen content in the oxygen-containing gas is preferably 20-100%, the flow rate of the oxygen-containing gas is 0.05-2.5L/min, and the temperature of the electrolysis reaction is preferably 55-75 ℃.
Further, the electrolytic reaction in step S1 is performed in stages, and the electrolytic reaction in this stage is stopped each time the nickel content in the nickel-rich solution reaches 40 to 50g/L, and the electrolytic reaction is continued by adding an electrolyte after separating the nickel-rich solution until a residual anode is formed.
Further, the electrolysis system is divided into an anode reaction zone and a cathode reaction zone, the anode reaction zone comprises electrolyte and an anode, the cathode reaction zone comprises electrolyte and a cathode, preferably, the liquid level of the electrolyte in the anode reaction zone is higher than that of the electrolyte in the cathode reaction zone by 3-5 cm, and preferably, during the electrolysis reaction, H in the electrolyte in the anode reaction zone is + The concentration is kept between 1 and 2mol/L, the volume concentration of hydrogen peroxide is kept between 1 and 10 percent, the concentration of copper ions is kept between 5 and 15g/L, the concentration of manganese ions is kept between 5 and 15g/L, and H in electrolyte in a cathode reaction zone is preferably selected in the electrolytic reaction process + The concentration is kept between 1 and 2mol/L, and the volume concentration of the hydrogen peroxide is kept between 1 and 10 percent.
Further, the step S2 includes: crushing the anode scrap, and mixing the crushed anode scrap with a nickel-rich solution to obtain a dispersion liquid, wherein the weight content of particles with the particle size of less than or equal to 400 meshes in the crushed anode scrap is preferably 60-80%; and (3) performing oxygen pressure leaching on the dispersion to obtain a leaching solution containing nickel and leaching slag, wherein the dispersion preferably further contains hydrogen peroxide, and the solid-to-liquid ratio in the dispersion is preferably 2-10g.
Further, in the oxygen pressure leaching process, the leaching oxygen partial pressure is 0.05-0.5 Mpa, the leaching temperature is 150-220 ℃, and preferably, the content of sulfuric acid in the leaching solution is 10-20 g/L at the end of leaching.
Further, the smelting method also comprises a recovery process of the leached slag, and the preferred recovery process comprises the following steps: and oxidizing and sintering the leached residues to obtain the metal oxide.
Further, the smelting method also comprises a process of removing impurities from the leaching solution, wherein the impurity removing process comprises the following steps: step A1, adjusting the pH value of the leachate to 1.5-3, preferably adjusting the pH value of the leachate by adopting a metal oxide; step A2, heating the leaching solution with the pH value of 1.5-3 to obtain nickel-rich slurry; step A3, carrying out solid-liquid separation on the nickel-rich slurry to obtain impurity precipitates and a nickel-rich liquid; and A4, purifying the nickel-rich liquid to obtain nickel salt.
Further, in the step A2, the heating temperature is 70 to 90 ℃ and the heating time is 0.5 to 1 hour, and the pH value of the leachate is preferably maintained at 1.5 to 3 during the heating process.
Further, the step A4 includes: extracting the nickel-rich liquid to obtain raffinate and nickel-containing extract, wherein the raffinate preferably contains copper ions and manganese ions and provides at least part of the copper ions and the manganese ions for electrolyte, and an extracting agent adopted in the extraction comprises a P204 extracting agent; carrying out back extraction treatment on the nickel-containing extraction liquid to obtain a nickel salt solution; and crystallizing the nickel salt solution to obtain the nickel salt.
By applying the technical scheme of the invention, firstly, the anode comprising the high nickel matte is electrolyzed, so that most of nickel in the high nickel matte enters into the electrolyte, and when the anode can not react continuously any more, a nickel-rich solution with high nickel content and a residual anode are correspondingly obtained. And then, carrying out oxygen pressure leaching on the anode scrap to further enable nickel in the anode scrap to enter the liquid, and further increasing the amount of the nickel separated from the raw material. In the oxygen pressure leaching process, not only nickel enters the leaching solution, but also impurity ions such as copper, iron, cobalt and the like enter the leaching solution, and because of the reduction potential difference among elements, particularly the reduction potential of nickel is low, the impurity ions with high reduction potential in the leaching solution are subjected to reduction replacement with nickel, so that the impurity ions remain in the leaching slag as sulfides, and the nickel, the sulfur and the impurity ions are effectively separated. By utilizing the smelting method, the sulfur and the nickel in the high nickel matte can be effectively separated through two steps, the process is simplified while the higher separation efficiency is ensured, and the cost is effectively reduced.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
According to the technical background of the application, the electrolysis process of the high nickel matte anode in the prior art has the problems of complex process and high cost, and in order to solve the problems, the application provides a high nickel matte hydrometallurgy method, which comprises the following steps: step S1, electrolyzing the anode containing high nickel matte to obtain a nickel-rich solution and a residual anode; and S2, carrying out oxygen pressure leaching on the anode scrap to obtain nickel-containing leachate and leaching residues.
By the smelting method, firstly, the anode containing high nickel matte is electrolyzed, so that most of nickel in the high nickel matte enters into the electrolyte, and when the anode can not react continuously any more, a nickel-rich solution with high nickel content and a residual anode are obtained correspondingly. And then, carrying out oxygen pressure leaching on the anode scrap to further enable the nickel in the anode scrap to enter the liquid, and further increasing the nickel content separated from the raw material. In the oxygen pressure leaching process, not only nickel enters the leaching solution, but also impurity ions such as copper, iron, cobalt and the like enter the leaching solution, and because of the reduction potential difference among elements, particularly the reduction potential of nickel is low, the impurity ions with high reduction potential in the leaching solution are subjected to reduction replacement with nickel, so that the impurity ions remain in the leaching slag as sulfides, and the nickel, the sulfur and the impurity ions are effectively separated. By utilizing the smelting method, the sulfur and the nickel in the high nickel matte can be effectively separated through two steps, the process is simplified while the higher separation efficiency is ensured, and the cost is effectively reduced.
In some embodiments, the step S1 includes: making an electrolysis system comprising a cathode, an electrolyte and an anode produce an electrolytic reaction to obtain a nickel-rich solution and a residual anode, wherein H in the electrolyte + The concentration is 1-2 mol/L, the volume concentration of hydrogen peroxide is 1-10%, the concentration of copper ions is 5-15 g/L, and the concentration of manganese ions is 5-15 g/L. By regulating H in the electrolyte + The concentration and the concentration of hydrogen peroxide enable the electrolyte to have stronger acidity and oxidability; and the manganese ions and the copper ions have a displacement reaction with the nickel ions in the electrolyte, so that more nickel ions enter the electrolyte, and copper and manganese form sulfide precipitates to be separated from nickel in the form of anode mud, so that the high nickel matte has a catalytic oxidation reaction, and the nickel in the high nickel matte is effectively electrolyzed into a solution from the anode. And, the setting of the above numerical range can further improve the effect of nickel separation, and if the concentrations of manganese ions and copper ions exceed the above range,resulting in excessive manganese ions and copper ions remaining in the electrolyte after the electrolytic reaction. Preferably, the electrolyte also contains sodium chloride, the concentration of the sodium chloride is 50-120 g/L, the sodium chloride in the concentration range can provide sufficient electrolyte for the electrolyte, so that the impedance of the electrolyte is low in the electrolytic process, the problem that the viscosity of the electrolyte is increased to cause obstruction to anodic electrolysis due to the excessive concentration of the sodium chloride is avoided, and the electrolytic reaction is ensured to maintain a high rate. The acid for adjusting the pH of the electrolyte may be selected from commonly used acids, such as hydrochloric acid, sulfuric acid or nitric acid, and preferably H in the electrolyte, in order to avoid the generation of harmful gases during the reaction and to ensure the stability of the system + Provided by sulfuric acid.
The setting method of the electrolysis system and the parameter setting in the electrolysis process can be designed by selecting a common method in the field, in order to improve the smelting efficiency, a plurality of anodes and cathodes are preferably selected, the homopolar center distance of each anode and cathode is 10-30 cm, and a plurality of anodes and cathodes are adopted for electrolysis, so that the contact area of the anodes and electrolyte is improved, and the electrolysis efficiency is further improved. In some embodiments, the anode current density is 200 to 350A/m 2 The electrolytic voltage is 2.8-4.0V. Under the conditions, the anode can be electrolyzed uniformly and rapidly, and the efficiency of the smelting method is effectively improved. In order to make more nickel in the high nickel matte be oxidized and enter the electrolyte, the electrolysis reaction is preferably carried out in oxygen-containing gas, the oxygen content in the oxygen-containing gas is preferably 20-100%, and the flow rate of the oxygen-containing gas is 0.05-2.5L/min, so that the chemical catalytic oxidation is simultaneously carried out on the basis of the electrocatalytic oxidation, and the dissolution rate of the nickel from the anode to the electrolyte is improved. The oxygen flow is too low, which can cause the reaction to slow down and be too large, and can cause the liquid level of the electrolytic bath to fluctuate, and the electrolytic reaction is not used to be carried out stably. The temperature of the electrolysis reaction is preferably 55-75 ℃, and the reaction speed is too slow when the temperature is lower than the range, and the temperature is higher than the range or causes a great amount of evaporation loss of water in an electrolytic bath during the electrolysis process, so that more acid mist is generated and pollution is caused.
Since the speed of the electrolytic reaction is gradually decreased as the nickel concentration in the electrolytic solution is gradually increased as the reaction proceeds, it is preferable that the electrolytic reaction in step S1 is performed in stages, the electrolytic reaction in this stage is stopped each time the nickel content in the nickel-rich solution reaches 40 to 50g/L, the nickel-rich solution is separated, and then a fresh electrolytic solution is added to continue the electrolytic reaction until a residual anode is formed. Monitoring the nickel content in the electrolyte in the electrolytic process, stopping the electrolytic reaction when the nickel content reaches a threshold value in the interval of 40-50 g/L, and replacing new electrolyte for further electrolytic reaction. The electrolyte that is replaced is part of the nickel-rich solution. When the anode is unable to react further, the anode scrap is obtained.
In order to further improve the stability of the reaction and to make the reaction at the anode less disturbed, it is preferable that the above-mentioned electrolysis system is divided into an anode reaction zone and a cathode reaction zone, the anode reaction zone includes the electrolyte and the anode, and the cathode reaction zone includes the electrolyte and the cathode. The method of dividing the electrolyte system into an anodic reaction zone and a cathodic reaction zone can be selected by one skilled in the art from the prior art by preferably placing the anode and a portion of the electrolyte in an anode bag, placing the cathode and another portion of the electrolyte in the cell, and placing the anode bag in the cell to form a separation of the anode and cathode. The electrolytic cell can be further divided into an anode chamber and a cathode chamber, the anode is sleeved in the anode chamber filled with the electrolyte, and the cathode is directly placed in the cathode chamber filled with the electrolyte, so as to further realize the separation effect.
The electrolyte in the anode reaction zone is communicated with the electrolyte in the cathode reaction zone through an anode bag, and preferably, the liquid level of the electrolyte in the anode reaction zone is 3-5 cm higher than that of the electrolyte in the cathode reaction zone, so that the electrolyte in the cathode reaction zone cannot flow into the anode reaction zone by virtue of static pressure difference, and the stability of the reaction environment in the anode reaction zone is ensured. Preferably, H in the electrolyte in the anode reaction zone during the electrolysis reaction + The concentration is kept between 1 and 2mol/L, the volume concentration of hydrogen peroxide is kept between 1 and 10 percent, the concentration of copper ions is kept between 5 and 15g/L, the concentration of manganese ions is kept between 5 and 15g/L, and H in electrolyte in a cathode reaction zone is preferably selected during the electrolytic reaction + The concentration is kept between 1 and 2mol/L, and the volume concentration of hydrogen peroxideThe reaction can be more stably carried out by keeping the reaction at 1% to 10%.
After electrolysis, there is also a portion of the nickel in the anode scrap that is not electrolyzed, at which point further nickel can be recovered by oxygen pressure leaching as described above. The oxygen pressure leaching may be referred to as a conventional oxygen pressure leaching process in the prior art, and in some embodiments of the present application, the step S2 includes: crushing the anode scrap, and mixing the crushed anode scrap with a nickel-rich solution to obtain a dispersion liquid, wherein the weight content of particles with the particle size of less than or equal to 400 meshes in the crushed anode scrap is preferably 60-80%; the dispersion liquid is subjected to oxygen pressure leaching to obtain leaching liquid containing nickel and leaching slag, and the nickel-rich solution has high acidity and contains more copper ions and manganese ions. On one hand, copper ions and manganese ions in the nickel-rich solution can be used as reducing agents, so that more nickel is leached; on the other hand, once the nickel in the anode scrap is leached, the sulfur in the nickel is also carried into the leaching solution, and at the moment, the copper ions in the nickel-rich solution can be used as a sulfur fixing agent to form copper sulfide, so that the sulfur is left in the leaching slag. The dispersion preferably further contains hydrogen peroxide, and the solid-to-liquid ratio in the dispersion is preferably 2 to 10g. The nickel in the anode scrap is further leached out by mixing the finely-divided anode scrap with the nickel-rich solution and further adding hydrogen peroxide to improve the concentration of the oxidant.
In order to further improve the nickel separation effect of the oxygen pressure leaching, preferably, during the oxygen pressure leaching, the leaching oxygen partial pressure is 0.05-0.5 Mpa, the leaching temperature is 150-220 ℃, after the oxygen pressure leaching, the residual acid content in the leaching solution is high, hydrogen ions in a leaching system are consumed along with the oxygen pressure leaching, and preferably, at the end of the leaching, the sulfuric acid content in the leaching solution is 10-20 g/L, so as to ensure the sufficient leaching of nickel and avoid excessive impurity ion leaching.
In some embodiments, the smelting method further comprises a recovery process of the leached slag, and preferably the recovery process comprises: and oxidizing and sintering the leaching slag to obtain the metal oxide. And (3) carrying out oxidation sintering on the leaching slag to desulfurize the leaching slag to obtain the metal oxide.
In order to obtain a nickel salt with less impurities, it is preferable that the smelting method further includes a process of removing impurities from the leachate, which includes: step A1, adjusting the pH value of the leaching solution to 1.5-3; step A2, heating the leaching solution with the pH value of 1.5-3 to obtain nickel-rich slurry; step A3, carrying out solid-liquid separation on the nickel-rich slurry to obtain impurity precipitates and a nickel-rich liquid; and A4, purifying the nickel-rich liquid to obtain nickel salt. As described above, the leachate of the present application contains a large amount of residual acid, and the impurity metal ions such as iron can be removed from the precipitation slag by adding an alkaline reagent to adjust the pH of the leachate and heating the leachate. Preferably, the pH of the leachate is adjusted by using the metal oxide so that nickel remaining in the metal oxide obtained by oxidizing and sintering the leaching residue is further introduced into the leachate, thereby improving the recovery rate of nickel.
In order to improve the effect and efficiency of precipitating and separating impurity metals such as iron, the heating temperature in the step A2 is preferably 70-90 ℃ for 0.5-1 h. The pH of the leachate is preferably maintained at a pH of 1.5 to 3 during heating. The pH of the leachate during heating may be maintained by the use of an alkaline agent produced, and in order to avoid the introduction of impurities which are not easily separable, it is preferred to carry out the pH adjustment by using one or both of sodium carbonate and sodium bicarbonate.
In some embodiments, it is preferable that the step A4 includes: extracting the nickel-rich liquid to obtain raffinate and nickel-containing extract, wherein the extracting agent adopted by the extraction comprises a P204 extracting agent; carrying out back extraction treatment on the nickel-containing extraction liquid to obtain a nickel salt solution; and crystallizing the nickel salt solution to obtain the nickel salt. The nickel salt is obtained by the extraction and crystallization treatment. When sulfuric acid is used for adjusting the pH value in the electrolytic reaction, the nickel salt is nickel sulfate. The nickel salt obtained by the smelting method has high purity, and can be used in the field of new energy. In order to further improve the recycling rate of the catalyst in the smelting method, the raffinate preferably contains copper ions and manganese ions, and the raffinate provides at least part of the copper ions and the manganese ions for the electrolyte.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
1) Casting a high nickel matte anode: the high nickel matte is cast into a 8cm by 10cm high nickel matte anode, and a 10cm by 10cm titanium plate is selected as a cathode to prepare electrolytic dissolution.
2) Electrolysis: and (3) sheathing an anode bag, and preparing electrolyte (containing 70g/L of sodium chloride, 100g/L of sulfuric acid, 2% hydrogen peroxide by volume concentration, 5g/L of copper ions and 7g/L of manganese ions). The electrolytic cell was filled with the electrolyte, and a plurality of anode bags and cathodes were placed in the electrolytic cell, wherein the center distance of homopolar was 20cm, and the liquid level in the anode bags was 3cm higher than the liquid level in the electrolytic cell. The electrolytic reaction is carried out by utilizing the electrolytic system, and the current density of the anode is controlled to be 230A/m 2 The voltage of the electrolytic cell is 3.0V, the temperature in the electrolytic cell is 60 ℃, oxygen is introduced into the anode bag at a speed of 0.1L/min, and the electrolytic cell is continuously stirred (at a stirring speed of 10 rpm) in the electrolytic process so as to keep the uniformity of the electrolyte in the reaction process. In the electrolytic process, the electrolyte is pumped out, and after a proper amount of sulfuric acid, hydrochloric acid and hydrogen peroxide are supplemented into the electrolyte, the part of the electrolyte is conveyed back to the electrolytic cell again, so that the concentrations of hydrogen ions, chloride ions and hydrogen peroxide in the electrolytic cell are basically kept unchanged in the reaction process. And then continuously injecting electrolyte (comprising 70g/L of sodium chloride, 100g/L of sulfuric acid, 2% hydrogen peroxide by volume concentration, 5g/L of copper ions and 7g/L of manganese ions) into the anode bag, keeping the liquid level difference of the anode bag and the cathode at 3cm, and keeping the concentrations of the chloride ions, the hydrogen ions, the copper ions, the manganese ions and the hydrogen peroxide in the anode bag unchanged. When the nickel content in the solution in the electrolytic bath reaches 50g/L, the electrolysis is stopped, and the solution is extracted to obtain a part of nickel-rich solution. Adding new electrolyte to continuously carry out the electrolytic reaction until the anode becomes a residual anode, and mixing the electrolyte with the extracted nickel content of 50g/L to obtain a nickel-rich solution.
3) And (3) electrolytic anode scrap crushing: and taking out the anode scrap, washing with water, and carrying out ball milling and crushing to ensure that the crushed anode scrap reaches 70% of particles below 400 meshes finally.
4) Pressure leaching: mixing and crushing the residual anode, the nickel-rich solution and hydrogen peroxide to ensure that the solid-liquid ratio reaches 5g (1L), and carrying out oxygen pressure leaching for 2h at the temperature of 150 ℃ and under the condition of 0.1Mpa of oxygen partial pressure to obtain leachate and leaching slag. The concentration of sulfuric acid in the leaching solution is 10g/L.
5) And (3) leaching residue desulfurization: and drying the leached slag, putting the leached slag into a furnace, heating to 950 ℃, introducing air (the flow is 1L/min), oxidizing and roasting for 2 hours, and obtaining the metal oxide.
6) Removing impurities: adding the metal oxide obtained in the step 5) into the leachate, adjusting the pH value to 2, heating to 80 ℃, reacting for 0.5h, continuously adding 10g/L sodium carbonate solution to maintain the pH value of the system to be 2, obtaining nickel-rich slurry, and carrying out solid-liquid separation to obtain iron-containing slag and nickel-rich liquid.
7) And (3) extracting the nickel-rich liquid by using a P204 extractant, and performing back extraction and crystallization treatment to obtain nickel sulfate crystals, wherein the leaching rate of nickel is 98.5%.
Example 2
1) Casting a high nickel matte anode: the high nickel matte is cast into a 8cm by 10cm high nickel matte anode, and a 10cm by 10cm titanium plate is selected as a cathode to prepare electrolytic dissolution.
2) Electrolysis: and (3) sheathing an anode bag, and preparing electrolyte (containing 90g/L of sodium chloride, 140g/L of sulfuric acid, hydrogen peroxide with the volume concentration of 4%, 10g/L of copper ions and 12g/L of manganese ions). The electrolytic cell was filled with the electrolyte, and a plurality of anode bags and cathodes were placed in the electrolytic cell, wherein the center distance of homopolar was 20cm, and the liquid level in the anode bags was 4cm higher than the liquid level in the electrolytic cell. The electrolytic reaction is carried out by utilizing the electrolytic system, and the current density of the anode is controlled to be 300A/m 2 The cell voltage was 3.5V, the temperature in the electrolytic cell was 65 ℃, 0.2L/min of oxygen was introduced into the anode bag, and the electrolytic cell was continuously stirred (stirring speed was 10 rpm) during the electrolysis process to keep the electrolyte homogeneous during the reaction. In the electrolytic process, the electrolyte is pumped out, and after a proper amount of sulfuric acid, hydrochloric acid and hydrogen peroxide is supplemented into the electrolyte, the electrolyte is re-conveyed back to the electrolytic cell, so that the concentrations of hydrogen ions, chloride ions and hydrogen peroxide in the electrolytic cell are basically maintained unchanged in the reaction process. Then continuously injecting electrolyte (comprising 70g/L sodium chloride, 100g/L sulfuric acid, 2% hydrogen peroxide by volume concentration, 5g/L copper ions and 7g/L manganese ions) into the anode bag, keeping the liquid level of the anode bag and the liquid level difference of the cathode at 4cm, and simultaneously enabling chloride ions and hydrogen ions in the anode bagThe concentrations of copper ions, manganese ions and hydrogen peroxide are kept unchanged. When the nickel content in the solution in the electrolytic cell reaches 45g/L, the electrolysis is stopped, and the solution is pumped out to obtain a part of nickel-rich solution. Adding new electrolyte to continuously carry out the electrolytic reaction until the anode becomes a residual anode, and mixing the extracted electrolyte with the nickel content of 45g/L to obtain a nickel-rich solution.
3) And (3) electrolytic anode scrap crushing: and taking out the anode scrap, washing with water, and carrying out ball milling and crushing to ensure that the crushed anode scrap reaches 70% of particles below 400 meshes finally.
4) Pressure leaching: mixing and crushing the anode scrap, the nickel-rich solution and hydrogen peroxide to ensure that the solid-to-liquid ratio reaches 6g 1L, and carrying out oxygen pressure leaching for 3h at the temperature of 180 ℃ and under the oxygen partial pressure of 0.2Mpa to obtain leachate and leaching slag. The concentration of sulfuric acid in the leaching solution is 15g/L.
5) And (3) leaching residue desulfurization: and drying the leached slag, putting the leached slag into a furnace, heating to 950 ℃, introducing air (the flow is 1L/min), oxidizing and roasting for 1h, and obtaining the metal oxide.
6) Removing impurities: adding the metal oxide obtained in the step 5) into the leachate, adjusting the pH value to 2.2, heating to 80 ℃, reacting for 0.5h, continuously adding 10g/L sodium carbonate solution to maintain the pH value of the system to be 2.2, obtaining nickel-rich slurry, and performing solid-liquid separation to obtain iron-containing slag and nickel-rich liquid.
7) Extracting the nickel-rich liquid by using a P204 extractant, and performing back extraction and crystallization treatment to obtain nickel sulfate crystals, wherein the leaching rate of nickel is 99.2%. And (3) recycling copper ions and manganese ions in the raffinate to the electrolyte in the step 2).
Example 3
1) Casting a high nickel matte anode: the high nickel matte is cast into a 8cm by 10cm high nickel matte anode, and a 10cm by 10cm titanium plate is selected as a cathode to prepare electrolytic dissolution.
2) Electrolysis: and (3) sheathing an anode bag, and preparing electrolyte (containing 100g/L of sodium chloride, 170g/L of sulfuric acid, 6% hydrogen peroxide by volume concentration, 15g/L of copper ions and 15g/L of manganese ions). The electrolytic cell was filled with the electrolyte, and a plurality of anode bags and cathodes were placed in the electrolytic cell, wherein the center distance of homopolar was 20cm, and the liquid level in the anode bags was 5cm higher than the liquid level in the electrolytic cell. Carrying out electrolytic reaction by using the electrolytic systemShould control the anode current density to 350A/m 2 The cell voltage was 4V, the temperature in the electrolytic cell was 70 ℃, oxygen gas was introduced into the anode bag while maintaining 0.35L/min, and the stirring was continued in the electrolytic cell during the electrolysis (stirring speed was 10 rpm) to maintain the uniformity of the electrolyte during the reaction. In the electrolytic process, the electrolyte is pumped out, and after a proper amount of sulfuric acid, hydrochloric acid and hydrogen peroxide is supplemented into the electrolyte, the electrolyte is re-conveyed back to the electrolytic cell, so that the concentrations of hydrogen ions, chloride ions and hydrogen peroxide in the electrolytic cell are basically maintained unchanged in the reaction process. And then continuously injecting electrolyte (comprising 70g/L of sodium chloride, 100g/L of sulfuric acid, 2% hydrogen peroxide by volume concentration, 5g/L of copper ions and 7g/L of manganese ions) into the anode bag, keeping the liquid level difference of the anode bag and the cathode at 5cm, and keeping the concentrations of the chloride ions, the hydrogen ions, the copper ions, the manganese ions and the hydrogen peroxide in the anode bag unchanged. When the nickel content in the solution in the electrolytic bath reaches 40g/L, the electrolysis is stopped, and the solution is pumped out to obtain partial nickel-rich solution. Adding new electrolyte to continuously carry out the electrolytic reaction until the anode becomes a residual anode, and mixing the electrolyte with the extracted nickel content of 40g/L to obtain a nickel-rich solution.
3) And (3) electrolytic anode scrap crushing: and taking out the anode scrap, washing with water, and carrying out ball milling and crushing to ensure that the crushed anode scrap particles below 400 meshes reach 80%.
4) Pressure leaching: mixing and crushing the anode scrap, the nickel-rich solution and hydrogen peroxide to ensure that the solid-to-liquid ratio reaches 8g 1L, and carrying out oxygen pressure leaching for 5h at the temperature of 200 ℃ and the oxygen partial pressure of 0.4Mpa to obtain leachate and leaching slag. The concentration of the sulfuric acid in the leaching solution is 20g/L.
5) And (3) leaching residue desulfurization: and drying the leached slag, putting the leached slag into a furnace, heating to 950 ℃, introducing air (the flow is 1L/min), oxidizing and roasting for 3 hours, and obtaining metal oxide.
6) Removing impurities: adding the metal oxide obtained in the step 5) into the leachate, adjusting the pH value to 1.8, heating to 80 ℃, reacting for 1h, continuously adding 10g/L sodium carbonate solution to maintain the pH value of the system to be 1.8, obtaining nickel-rich slurry, and carrying out solid-liquid separation to obtain iron-containing slag and nickel-rich liquid.
7) And (3) extracting the nickel-rich liquid by using a P204 extractant, and performing back extraction and crystallization treatment to obtain nickel sulfate crystals, wherein the leaching rate of nickel is 99.8%. And (3) recycling copper ions and manganese ions in the raffinate to the electrolyte in the step 2).
Example 4
The difference from example 1 is that the temperature in the cell in step 2) was 55 ℃.
Example 5
The difference from example 1 is that the temperature in the electrolytic cell in step 2) is 75 ℃.
Example 6
The difference from example 1 is that the temperature in the cell in step 2) was 45 ℃.
Example 7
The difference from example 1 is that the temperature in the cell in step 2) is 90 ℃.
Example 8
The difference from example 1 is that the flow rate of oxygen in step 2) was 0.05L/min.
Example 9
The difference from example 1 is that the flow rate of oxygen in step 2) was 2.5L/min.
Example 10
The difference from example 1 is that the flow rate of oxygen in step 2) was 0.02L/min.
Example 11
The difference from example 1 is that the flow rate of oxygen in step 2) was 3.0L/min.
Example 12
The difference from example 1 is that the concentration of manganese ions in step 2) is 5g/L.
Example 13
The difference from example 1 is that the concentration of manganese ions in step 2) was 15g/L.
Example 14
The difference from example 1 is that the concentration of manganese ions in step 2) is 2g/L.
Example 15
The difference from example 1 is that the concentration of manganese ions in step 2) is 18g/L.
Example 16
The difference from example 1 is that the oxygen partial pressure in step 4) is 0.05MPa.
Example 17
The difference from example 1 is that the oxygen partial pressure in step 4) is 0.5MPa.
Example 18
The difference from example 1 is that the oxygen partial pressure in step 4) is 0.02MPa.
Example 19
The difference from example 1 is that the oxygen partial pressure in step 4) is 0.6MPa.
Example 20
The difference from example 1 is that the leaching temperature in step 4) is 220 ℃.
Example 21
The difference from example 1 is that the leaching temperature in step 4) is 120 ℃.
Example 22
The difference from example 1 is that the leaching temperature in step 4) is 250 ℃.
Example 23
The difference from the example 1 is that the solid-liquid ratio in the step 4) is 2g.
Example 24
The difference from example 1 is that the solid-liquid ratio in step 4) is 10g.
Example 25
The difference from the example 1 is that the solid-liquid ratio in the step 4) is 1g.
Example 26
The difference from example 1 is that the solid-liquid ratio in step 4) is 15g.
Example 27
The difference from example 1 is that the reaction is carried out in step 6) by heating to 70 ℃.
Example 28
The difference from example 1 is that the reaction is carried out in step 6) by heating to 90 ℃.
Example 29
The difference from example 1 is that the reaction is carried out in step 6) by heating to 60 ℃.
Example 30
The difference from example 1 is that the reaction is carried out in step 6) by heating to 95 ℃.
Example 31
The difference from example 1 is that in step 4), the anode scrap is mixed with a solution containing 100g/L sodium chloride, 170g/L sulfuric acid, 6% by volume hydrogen peroxide, 15g/L copper ions and 15g/L manganese ions, and the mixture is subjected to oxygen pressure leaching at 200 ℃ and 0.4MPa oxygen partial pressure for 5 hours to obtain a leaching solution and leaching residues. The concentration of the sulfuric acid in the leaching solution is 20g/L.
The nickel leaching rates for the above examples are shown in table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the smelting method, firstly, the anode comprising the high nickel matte is electrolyzed, so that most of nickel in the high nickel matte enters into the electrolyte, and when the anode can not react continuously any more, a nickel-rich solution with high nickel content and a residual anode are obtained correspondingly. And then, carrying out oxygen pressure leaching on the anode scrap to further enable the nickel in the anode scrap to enter the liquid, and further increasing the nickel content separated from the raw material. In the oxygen pressure leaching process, not only nickel enters the leaching solution, but also impurity ions such as copper, iron, cobalt and the like in the leaching solution enter the leaching solution, and because of the reduction potential difference among elements, particularly the reduction potential of nickel is low, the impurity ions with higher reduction potential in the leaching solution are subjected to reduction displacement with nickel, so that the impurity ions are remained in the leaching slag as sulfides, and the nickel, the sulfur and the impurity ions are effectively separated. By utilizing the smelting method, the sulfur and the nickel in the high nickel matte can be effectively separated through two steps, the process is simplified while the higher separation efficiency is ensured, and the cost is effectively reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The high nickel matte hydrometallurgy method is characterized by comprising the following steps:
step S1, electrolyzing the anode containing the high nickel matte to obtain a nickel-rich solution and a residual anode;
s2, carrying out oxygen pressure leaching on the anode scrap to obtain nickel-containing leachate and leaching residues;
in the oxygen pressure leaching process, the leaching oxygen partial pressure is 0.05 to 0.5Mpa, and the leaching temperature is 150 to 220 ℃; the step S2 includes: crushing the residual anode, and mixing the crushed residual anode with the nickel-rich solution to obtain a dispersion liquid, wherein the weight content of particles with the particle size of less than or equal to 400 meshes in the crushed residual anode is 60-80%; carrying out oxygen pressure leaching on the dispersion liquid to obtain leaching liquid containing nickel and leaching slag, wherein the dispersion liquid also contains hydrogen peroxide, and the solid-to-liquid ratio in the dispersion liquid is (2) - (10g);
the step S1 includes:
subjecting an electrolysis system comprising a cathode, an electrolyte and the anode to the electrolysis reaction to obtain the nickel-rich solution and the residual anode, wherein H is in the electrolyte + The electrolyte comprises 1 to 2mol/L of hydrogen peroxide, 1 to 10 percent of volume concentration of hydrogen peroxide, 5 to 15g/L of copper ions, 5 to 15g/L of manganese ions, sodium chloride and H, wherein the concentration of the sodium chloride in the electrolyte is 50 to 120g/L, and the volume concentration of the hydrogen peroxide in the electrolyte is 1 to 2mol/L + Provided by sulfuric acid;
the number of the anodes and the number of the cathodes are multiple, the homopolar center distance of each anode and each cathode is 10 to 30cm, and the current of each anode is denseThe degree is 200 to 350A/m 2 And the electrolytic voltage is 2.8 to 4.0V, the electrolytic reaction is carried out in oxygen-containing gas, the content of oxygen in the oxygen-containing gas is 20 to 100 percent, the flow rate of the oxygen-containing gas is 0.05 to 2.5L/min, and the temperature of the electrolytic reaction is 55 to 75 ℃.
2. The nickel matte hydrometallurgical method according to claim 1, wherein the electrolytic reaction in step S1 is performed in stages, the electrolytic reaction in this stage is stopped every time the nickel content in the nickel-rich solution reaches 40 to 50g/L, the nickel-rich solution is separated, and then the electrolyte is added to continue the electrolytic reaction until the anode scrap is generated.
3. The high nickel matte hydrometallurgical method of claim 1, wherein the electrolysis system is divided into an anode reaction zone and a cathode reaction zone, the anode reaction zone comprising the electrolyte and the anode, and the cathode reaction zone comprising the electrolyte and the cathode.
4. The hydrometallurgical method for nickel matte according to claim 3, wherein the liquid level of the electrolyte in the anode reaction zone is 3 to 5cm higher than that in the cathode reaction zone.
5. The hydrometallurgical process for high nickel matte according to claim 4, wherein during the electrolytic reaction, H in the electrolyte of the anodic reaction zone is present + The concentration is kept between 1 and 2mol/L, the volume concentration of hydrogen peroxide is kept between 1 and 10 percent, the concentration of copper ions is kept between 5 and 15g/L, and the concentration of manganese ions is kept between 5 and 15g/L; h in the electrolyte in the cathode reaction zone in the electrolytic reaction process + The concentration is kept between 1 and 2mol/L, and the volume concentration of hydrogen peroxide is kept between 1 and 10 percent.
6. The nickel freematte hydrometallurgy method according to claim 1, wherein the content of sulfuric acid in the leachate is 10-20 g/L at the end of leaching.
7. The high nickel matte hydrometallurgical method according to claim 1, wherein the smelting method further comprises a recycling process of the leached slag, the recycling process comprising: and oxidizing and sintering the leaching slag to obtain the metal oxide.
8. The nickel-high matte hydrometallurgical method according to claim 7, wherein the smelting method further comprises a process of impurity removal of the leachate, the impurity removal process comprising:
step A1, adjusting the pH value of the leachate to 1.5 to 3;
step A2, heating the leachate with the pH value of 1.5 to 3 to obtain nickel-rich slurry;
step A3, carrying out solid-liquid separation on the nickel-rich slurry to obtain impurity precipitates and a nickel-rich liquid;
and A4, purifying the nickel-rich liquid to obtain nickel salt.
9. The nickel matte blast process according to claim 8, wherein the metal oxide is used to adjust the pH of the leachate.
10. The nickel matte hydrometallurgy method according to claim 8, wherein in the step A2, the heating temperature is 70 to 90 ℃ and the heating time is 0.5 to 1h.
11. The nickel matte hydrometallurgy method according to claim 10, wherein the pH of the leachate is maintained at 1.5 to 3 during the heating process.
12. The high nickel matte hydrometallurgical method of claim 8, wherein step A4 comprises:
extracting the nickel-rich liquid to obtain raffinate and nickel-containing extract, wherein the raffinate contains copper ions and manganese ions and provides at least part of the copper ions and the manganese ions for the electrolyte, and an extracting agent adopted by the extraction comprises a P204 extracting agent;
carrying out back extraction treatment on the nickel-containing extraction liquid to obtain a nickel salt solution;
and crystallizing the nickel salt solution to obtain the nickel salt.
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| CN101560670A (en) * | 2009-05-20 | 2009-10-21 | 北京矿冶研究总院 | High nickel matte refining method |
| CN102154545A (en) * | 2011-05-26 | 2011-08-17 | 中国地质科学院矿产综合利用研究所 | Low nickel matte high-temperature oxygen pressure water leaching process |
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| CN106283128A (en) * | 2016-08-04 | 2017-01-04 | 浙江工业大学义乌科学技术研究院有限公司 | A kind of method of electrolytic preparation bright nickel in alkaline electrolyte |
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| CN101560670A (en) * | 2009-05-20 | 2009-10-21 | 北京矿冶研究总院 | High nickel matte refining method |
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| CN107604170A (en) * | 2017-08-25 | 2018-01-19 | 金川集团股份有限公司 | A kind of method of separation and concentration noble metal in potassium cloride slag from low nickel matte |
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